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| United States Patent |
5,779,781
|
|
Gregory
, et al.
|
July 14, 1998
|
Ink and toner compositions containing substituted phenyl AZO thiophene
dye
Abstract
An ink composition comprising:
(i) a medium comprising a low melting point solid, an organic solvent, or a
mixture of water and one or more water-soluble organic solvent(s); and
(ii) an azothiophene of Formula (1):
##STR1##
wherein: R, R.sup.1, R.sup.2 and R.sup.3 each independently is optionally
substituted alkyl or alkenyl.
Also claimed are inks containing mixtures of the azothiophene of Formula
(1) with other azothiophenes and with azo dyes, a process for ink jet
printing of textiles using the inks, a process for ink jet printing a
substrate with the inks and toner resin composition containing an
azothiophene of Formula (1).
| Inventors:
|
Gregory; Peter (Manchester, GB);
Leaver; Alan Thomas (Manchester, GB)
|
| Assignee:
|
Zeneca Limited (London, GB2)
|
| Appl. No.:
|
831934 |
| Filed:
|
April 2, 1997 |
Foreign Application Priority Data
| Current U.S. Class: |
106/31.51; 427/394 |
| Intern'l Class: |
C09D 011/02 |
| Field of Search: |
106/31.51
427/394
|
References Cited
U.S. Patent Documents
| 4207067 | Jun., 1980 | Becker | 106/31.
|
| 4212642 | Jul., 1980 | Della Casa et al. | 106/31.
|
| 4401692 | Aug., 1983 | Schickfluss et al. | 106/31.
|
| 4422854 | Dec., 1983 | Hahnle et al. | 106/31.
|
| 5389596 | Feb., 1995 | Etzbach et al. | 106/31.
|
| Foreign Patent Documents |
| 0 297 710 A1 | Jan., 1989 | EP | .
|
| 0 347 685 A2 | Dec., 1989 | EP | .
|
| 0 347 685 A3 | Dec., 1989 | EP | .
|
| 0 392 358 A1 | Oct., 1990 | EP | .
|
| 0 588 489 A1 | Mar., 1994 | EP | .
|
| 0 671 440 A2 | Sep., 1995 | EP.
| |
| 23 04 203 | Aug., 1973 | DE | .
|
| 55-92766 A | Jul., 1980 | JP | .
|
| 55-118964 A | Sep., 1980 | JP | .
|
| 1 394 365 | May., 1975 | GB | .
|
| WO 83/02452 | Jul., 1983 | WO | .
|
| WO 97/04030 | Feb., 1997 | WO | .
|
Other References
Chemical Abstracts, vol. 94, No. 10, Oct. 3, 1981, Mitsubishi Chemical Co.
Ltd.
Chemical Abstracts, vol. 94, No. 1, May 1, 1981, Mitsubishi Chemical Co.
Ltd.
|
Primary Examiner: Klemanski; Helene
Attorney, Agent or Firm: Pillsbury Madison & Sutro LLP
Claims
We claim:
1. An ink composition comprising:
(i) a medium comprising component (a), (b) or (c):
(a) a low melting point solid;
(b) an organic solvent selected from ketones, alkanols, esters, ethers,
amides, and a mixture of an aliphatic hydrocarbon and a polar solvent;
(c) a mixture of water and one or more water-soluble organic solvents(s),
wherein the weight ratio of water to water-soluble organic solvent is from
99:1 to 50:50; and
(ii) an azothiophene of Formula (1):
##STR11##
wherein: R, R.sup.1, R.sup.2 and R.sup.3 each independently is optionally
substituted alkyl or alkenyl.
2. An ink according to claim 1 wherein R, R.sup.1, R.sup.2 and R.sup.3 each
independently is alkyl or alkenyl.
3. An ink composition comprising:
(i) a medium as defined in claim 1; and p1 (ii) a mixture of dyes
comprising an azothiophene of Formula (1) as defined in claim 1 and an
azothiophene of Formula (4):
##STR12##
wherein: R.sup.4 is --CN, --Cl, --Br, --NO.sub.2, C.sub.1-4
-alkylcarbonyl, phenylcarbonyl, C.sub.1-4 -alkylsulphonyl, --COC.sub.1-4
-alkyl, --CONH.sub.2, --CONH(C.sub.1-4 -alkyl) or --CON(C.sub.1-4
-alkyl).sub.2 ;
R.sup.5 is --H, C.sub.1-4 -alkyl, phenyl or --COC.sub.1-4 -alkyl;
R.sup.6 is --H, C.sub.1-4 -alkyl, phenyl, NO.sub.2, --CN, --Cl, --Br,
--COC.sub.1-4 -alkyl, --CONH.sub.2, --CONH(C.sub.1-4 -alkyl) or
--CON(C.sub.1-4 -alkyl).sub.2 ;
R.sup.7 is --H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, --Cl, --Br,
--NHCOC.sub.1-4 -alkyl or --NHSO.sub.2 C.sub.1-4 -alkyl;
R.sup.8 is --H, C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy; and
R.sup.9 and R.sup.10 each independently is --H, C.sub.1-4 -alkyl, C.sub.2-4
-alkenyl or C.sub.1-4 -alkyl substituted by --OH, C.sub.1-4 -alkoxy, --CN,
phenyl, C.sub.1-4 -alkylCO--, C.sub.1-4 -alkoxyCO--, HOC.sub.1-4 -alkoxy,
C.sub.1-4 -alkoxy-C.sub.1-4 -alkoxy, C.sub.1-4 -alkoxy-C.sub.1-4
-alkoxyCO--,--Cl or C.sub.1-4 -alkoxyCOO.
4. An ink composition comprising: p1 (i) a medium comprising a low melting
point solid, an organic solvent,or a mixture of water and one or more
water-soluble organic solvent(s); and p1 (ii) a mixture of dyes comprising
an azothiophene of Formula (b 1) as defined in claim 1 and an azo compound
of Formula (5):
##STR13##
wherein: R.sup.11, R.sup.12 and R.sup.13 each independently is --CN,
--NO.sub.2, --Cl or --Br;
R.sup.14 is --H, C.sub.1-4 -alkyl, --Cl, --Br, --NHCOC.sub.1-4 -alkyl or
--NHSO.sub.2 C.sub.1-4 -alkyl;
R.sup.15 --H, C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy; p2 R.sup.9 and
R.sup.10 each independently is --H, C.sub.1-4 -alkyl, C.sub.2-4 -alkenyl
or C.sub.1-4 -alkyl substituted by --OH, C.sub.1-4 -alkoxy, --CN, phenyl,
C.sub.1-4 -alkylCO--, C.sub.1-4 -alkoxyCO--, HOC.sub.1-4 -alkoxy,
C.sub.1-4 -alkoxy-C.sub.1-4 -alkoxy, C.sub.1-4 -alkoxy-C.sub.1-4
-alkoxyCO--, --Cl or C.sub.1-4 -alkoxyCOO.
5. An ink composition according to any one of claims 1 to 4 wherein the
medium comprises water and one or more water-soluble organic
solvent(s),wherein the weight ratio of water to water-soluble organic
solvent is from 99:1 to 50:50.
6. An ink composition according to any one of claims 1 to 4 comprising:
(a) 0.5 to 20 parts of the dye(s);
(b) 2 to 60 parts of water-soluble organic solvent(s);
(c) 1 to 95 parts water;
(d) 0.5 to 20 parts dispersing agent; and
(e) 0.05 to 2 parts defoamer;
wherein the parts (a)+(b)+(c)+(d)+(e)=100.
7. An ink composition according to any one claims 1 to 4 wherein the ink
composition has a pH of less than 7.
8. An ink jet printing process for printing a substrate with an ink
composition comprising forming the ink into small droplets by ejection
from a reservoir through a small orifice so that the droplets of ink are
directed at the substrate wherein the ink composition comprises: p1 (i) a
medium comprising a low melting point solid, an organic solvent, or a
mixture of water and one or more water-soluble organic solvent(s); and p1
(ii) a dye or mixture of dyes as defined in any one of claims 1 to 4.
9. A paper, an overhead projector slide or a textile material printed by
means of the process according to claim 8.
10. A process for the coloration of a textile material with an ink
composition which comprises the steps:
i) applying the ink composition to the textile material by ink jet
printing, and
ii) heating the textile material at a temperature from 50.degree. C. to
250.degree. C. to fix the dye on the material, wherein the ink composition
comprises:
(a) a medium comprising a low melting point solid, an organic solvent, or a
mixture of water and one or more water-soluble organic solvent(s); and
(b) a dye or mixture of dyes as defined in any one of claims 1 to 4.
11. A textile material coloured by means of the process according to claim
10.
12. A toner resin composition comprising a toner resin and a dye, wherein
the dye is of Formula (1), a mixture of dyes of Formulae (1) and (4), or a
mixture of dyes of Formulae (1) and (5), wherein said dyes are as defined
in any one of claims 1 to 4.
13. An ink composition according to claim 4 wherein the medium comprises
water and one or more water-soluble organic solvent(s).
Description
The present invention relates to compositions and solutions thereof,
suitable for use in printing and imaging technologies, especially those
suitable for coloration of substrates such as paper, plastics, textiles,
metal and glass by printing processes such as ink jet printing and those
suitable for use in electrophotography such as toners.
Ink jet printing is a non-impact printing technique which involves
ejecting, thermally or by action of an oscillating piezo crystal, droplets
of ink continuously or on demand from a fine nozzle directly onto a
substrate such as paper, plastics, textile, metal or glass. The ink may be
aqueous, solvent or hot melt based and must provide sharp, non-feathered
images which have good waterfastness, light fastness and optical density,
have fast fixation to the substrate and cause no clogging of the nozzle.
Electrophotographic copiers or printers generally comprise an organic
photoconductor (OPC) and a developer or toner. The OPC generally comprises
an electrically conducting support, a charge generating layer and a charge
transport layer. The electrically conducting support is a metal drum,
typically an aluminium drum, or a metallised polymer film, typically
aluminised polyester. The charge generating layer comprises a charge
generating material (CGM) and a binder resin, typically a polycarbonate.
The charge transport later comprises a charge transport material (CTM) and
a binder resin, typically a polycarbonate. The developer or toner
comprises a toner resin, a colorant and optionally a charge control agent
(CCA). The toner resin is typically a styrene or substituted styrene
polymer or styrene-butadiene copolymer. The colorant is typically a dye or
pigment or mixture thereof.
According to a first aspect of the present invention there is provided an
ink composition comprising:
(i) an azothiophene of Formula (b 1):
##STR2##
wherein: R, R.sup.1, R.sup.2 and R.sup.3 each independently is optionally
substituted alkyl or alkenyl; and
(ii) a medium comprising a low melting point solid, an organic solvent, or
a mixture of water and one or more water-soluble organic solvent(s). The
alkyl groups represented by R, R.sup.1, R.sup.2 and R.sup.3 are preferably
C.sub.1-12 -alkyl, more preferably C.sub.1-6 -alkyl and especially
C.sub.1-4 -alkyl each of which is optionally substituted. The alkyl groups
represented by R, R.sup.1, R.sup.2 and R.sup.3 may be straight or branched
chain alkyl groups. The alkenyl groups represented by R, R.sup.1, R.sup.2
and R.sup.3 are preferably C.sub.2-12 -alkenyl, more preferably C.sub.2-6
-alkenyl and especially C.sub.2-3 -alkenyl each of which is optionally
substituted.
When any of the groups R, R.sup.1,R.sup.2 and R.sup.3 are optionally
substituted, preferred substituents are selected from --OH, C.sub.1-4
-alkoxy, --CN, phenyl, C.sub.1-4 -alkylCO--, C.sub.1-4 -alkoxyC(O)O--,
C.sub.1-4-alkoxyCO--, HOC.sub.1-4 -alkoxyCO-- and phenyl substituted
by--OH, --NH.sub.2 or --NO.sub.2.
Preferred azothiophene dyes of Formula (b 1) are those in which R.sup.1 and
R.sup.2 each independently is C.sub.1-4 -alkyl or C.sub.2-3 -alkenyl and R
and R.sup.3 each independently is C.sub.1-4 -alkyl. An especially
preferred azothiophene of Formula (1) is that in which R.sup.1 and R.sup.2
are both ethyl and R and R.sup.3 are both methyl.
The dyes of Formula (1) may be prepared by diazotising a 2-aminothiophene
of Formula (2):
##STR3##
and coupling with an aromatic amine of Formula (3):
##STR4##
wherein: R, R.sub.1, R.sub.2 and R.sup.3 are as hereinbefore defined. The
diazotisation and coupling may be performed by conventionally used methods
and the azothiophenes may be isolated using known techniques.
The azothiophenes of Formula (1) exist in various crystalline modifications
and it is intended that the present definition of the azothiophenes
includes such crystalline modifications which may be formed by established
treatments such as heat treatment, solvent treatment, recrystallisation or
seeding.
According to a second aspect of the present invention there is provided an
ink composition comprising:
(i) a medium comprising a low melting point solid, an organic solvent, or a
mixture of water and one or more water-soluble organic solvent(s); and
(ii) a mixture of dyes comprising an azothiophene of Formula (b 1) and an
azothiophene of Formula (4):
##STR5##
wherein: R.sup.4 is --CN, --Cl, --Br, --NO.sub.2, C.sub.1-4
-alkylcarbonyl, phenylcarbonyl, C.sub.1-4 -alkylsulphonyl, --COC.sub.1-4
-alkyl, --CONH.sub.2, --CONH (C.sub.1-4 -alkyl) or --CON(C.sub.1-4
-alkyl).sub.2 ;
R.sup.5 is --H, C.sub.1-4 -alkyl, phenyl or --COC.sub.1-4 -alkyl;
R.sup.6 is --H, C.sub.1-4 -alkyl, phenyl, NO.sub.2, --CN, --Cl, --Br,
--COC.sub.1-4 -alkyl, --CONH.sub.2, --CONH(C.sub.1-4 -alkyl) or
--CON(C.sub.1-4 -alkyl).sub.2 ;
R.sup.7 is --H, C.sub.1-4 -alkyl, C.sub.1-4 --Cl, --Br, --NHCOC.sub.1-4
-alkyl or --NHSO.sub.2 C.sub.1-4 -alkyl;
R.sup.8 is --H, C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy; and
R.sup.9 and R.sup.10 each independently is --H, C.sub.1-4 -alkyl, C.sub.2-4
-alkenyl or C.sub.1-4 -alkyl substituted by --OH, C.sub.1-4 -alkoxy, --CN,
phenyl, C.sub.1-4 -alkylCO--, C.sub.1-4 -alkoxyCO--, HOC.sub.1-4
-alkoxy-C.sub.1-4 -alkoxy-C.sub.1-4 -alkoxy, C.sub.1-4 -alkoxy-C.sub.1-4
-alkoxyCO--,--Cl or C.sub.1-4 -alkoxyCOO.
Preferred dyes of Formula (b 4) are those in which R.sup.4 is --NO.sub.2,
--CN or C.sub.1-4 -alkylcarbonyl, R.sup.5 is --H or C.sub.1-4 alkyl,
R.sup.6 is --NO.sub.2 or --CN, R.sup.7 is C.sub.1-4 -alkyl or
--NHCOC.sub.1-4 -alkyl, R.sup.8 is --H or C.sub.1-4 -alkoxy, R.sup.9 and
R.sup.10 each independently is C.sub.1-4 -alkyl. Especially preferred dyes
of Formula (4) are those in which R.sup.4 is --NO.sub.2, R.sup.5 is --H,
R.sup.6 is --NO.sub.2, R.sup.7 is --CH.sub.3, --C.sub.2 H.sub.5,
--NHCOCH.sub.3, --NHCOC.sub.2 H.sub.5, --NHCOC.sub.3 H.sub.7 or
--NHCOCH(CH.sub.3).sub.3, R.sup.8 is --H or --OCH.sub.3 and R.sup.9 and
R.sup.10 are both --C.sub.2 H.sub.5.
The dye mixtures may be prepared as physical mixtures, by
co-crystallisation or co-synthesis.
Mixtures of dyes of Formulae (1) and (4) preferably comprise from 30% to
70% of a dye of Formula (1), and from 70% to 30% of a dye of Formula (4),
more preferably from 40% to 60% of a dye of Formula (1) and from 60% to
40% of a dye of Formula (4) and especially from 45% to 55% of a dye of
Formula (1) and from 55% to 45% of a dye of Formula (4).
According to a third aspect of the present invention there is provided an
ink composition comprising:
(i) a medium comprising a low melting point solid, an organic solvent, or a
mixture of water and one or more water-soluble organic solvent(s); and
(ii) a mixture of dyes comprising an azothiophene of Formula (1) and an azo
compound of Formula (5):
##STR6##
wherein: R.sup.11, R.sup.12 and R.sup.13 each independently is --CN,
--NO.sub.2, --Cl or --Br;
R.sup.14 is --H, C.sub.1-4 -alkyl, --Cl, --Br, --NHCOC.sub.1-4 -alkyl or
-NHSO.sub.2 C.sub.1-4 -alkyl;
R.sup.15 is --H, C.sub.1-4 -alkyl or C.sub.1-4 -alkoxy; and
R.sup.9 and R.sup.10 are as hereinbefore defined.
A first preferred dye of Formula (5) is that in which R.sup.11 and R.sup.13
are --CN, R.sup.12 is --NO.sub.2, R.sup.14 is --CH.sub.3, R.sup.15 is --H
and R.sup.9 and R.sup.10 are both --C.sub.2 H.sub.5.
A second preferred dye of Formula (5) is that in which R.sup.11 is --CN,
R.sup.12 is --NO.sub.2, R.sub.13 is --Br, R.sup.14 is --NHCOCH.sub.3,
R.sup.15 is --H and R.sup.9 and R.sup.10 are both --C.sub.2 H.sub.5.
Mixtures of dyes of Formula (1) and (5) preferably comprise from 5% to 50%
of a dye of Formula (1) and from 95% to 50% of a dye of Formula (5), more
preferably from 10% to 45% of a dye of Formula (1) and from 90% to 55% of
a dye of Formula (5).
A first preferred mixture of dyes comprise from 5% to 15% a dye of Formula
(1) in which R.sup.1 and R.sup.2 each independently is C.sub.1-4 -alkyl
preferably methyl or ethyl, or C.sub.2-3 alkenyl and R and R.sup.3 each
independently is C.sub.1-4 -alkyl preferably methyl or ethyl, and from 95%
to 85% of a dye of Formula (5) in which R.sup.11 is --CN, R.sup.12 is
--NO.sub.2, R.sup.13 is --Br, R.sup.14 is --NHCOCH.sub.3, R.sup.15 is --H
and R.sup.9 and R.sup.10 are both --C.sub.2 H.sub.5.
A second preferred mixture of dyes comprises from 35% to 45% of a dye of
Formula (1) in which R.sup.1 and R.sup.2 each independently is C.sub.1-4
-alkyl preferably methyl or ethyl, or C.sub.2-3 -alkenyl and R and R.sup.3
each independently is C.sub.1-4 -alkyl preferably methyl or ethyl, and
from 65% to 55% of a dye of Formula (5) in which R.sup.11 and R.sup.13 are
--CN, R.sup.12 is --NO.sub.2, R.sup.14 is --CH.sub.3, R.sup.15 is --H and
R.sup.9 and R.sup.10 are both --C.sub.2 H.sub.5.
The ink compositions of the present invention preferably contain from 0.5%
to 20%, more preferably from 0.5% to 15%, and especially from 1% to 3%, by
weight of the dye of Formula (1) or mixtures of dyes of Formulae (1) and
(4) or mixture of dyes of Formulae (1) and (5) based on the total weight
of the ink.
The medium for the ink compositions of the first, second and third aspects
of the present invention may be a liquid or a low melting point solid.
Liquid media are preferably a mixture of water and one or more
water-soluble organic solvent(s), or an organic solvent. Aqueous-based ink
compositions are generally used in office or home printers whereas solvent
based ink compositions find use in industrial continuous printers.
It is preferred that the dye of Formula (1) and the mixtures of dyes of
Formulae (1) and (4) and of Formulae (1) and (5) are finely dispersed in
the medium, or more preferably are dissolved completely in the medium to
form a solution.
Where the liquid medium comprises a mixture of water and one or more
water-soluble organic solvent(s), it is preferred that the weight ratio of
water to water-soluble organic solvent(s) is from 99:1 to 1:99, more
preferably from 99:1 to 50:50 and especially from 95:5 to 80:20. The
water-soluble organic solvent(s) is preferably selected from C.sub.1-4
-alkanols, for example methanol, ethanol, n-propanol, isopropanol,
n-butanol, sec-butanol, tert-butanol and isobutanol; cyclic alkanols, for
example cyclohexanol and cyclopentanol; amides, for example
dimethylformamide and dimethylacetamide; ketones or ketone-alcohols, for
example acetone and diacetone alcohol; ethers, for example tetrahydrofuran
and dioxane; oligo- or poly-alkyleneglycols, for example diethylene
glycol, triethylene glycol, polyethylene glycol and polypropylene glycol;
alkyleneglycols or thioglycols containing a C.sub.2 -C.sub.6 -alkylene
group, for example ethylene glycol, propylene glycol, butylene glycol,
pentylene glycol, hexylene glycol and thiodiglycol; polyols, for example
glycerol and 1 ,2,6-hexanetriol; C.sub.1-4 -alkyl-ethers of polyhydric
alcohols, for example 2-(2-methoxyethoxy)ethanol,
2-(2-ethoxyethoxy)-ethanol, 2-›2-(2-methoxyethoxy)ethoxy!ethanol and
2-›2-(2-ethoxyethoxy)-ethoxy!-ethanol; heterocyclic ketones, for example
2-pyrrolidone and N-methyl-2-pyrrolidone; or mixtures containing two or
more of the aforementioned water-soluble organic solvents, for example
thiodiglycol and a second glycol or diethylene glycol and 2-pyrrolidone.
Preferred water-soluble organic solvents are 2-pyrrolidone;
N-methyl-pyrrolidone;
alkylene- and oligo-alkylene-glycols, for example ethyleneglycol,
diethyleneglycol, triethyleneglycol; and lower alkyl ethers of polyhydric
alcohols such as or 2-methoxy-2-ethoxy 2-ethoxyethanol; and
polyethyleneglycols with a molecular weight of up to 500. A preferred
specific solvent mixture is a binary or ternary mixture of water and
diethylene glycol and/or, 2-pyrrolidone or N-methylpyrrolidone in weight
ratios 75-95:25-5 and 60-80:0-20:0-20 respectively.
When the medium comprises a mixture of water and one or more water-soluble
organic solvent(s), it preferably also contains humectant to inhibit
evaporation of water and preservative to inhibit the growth of fungi,
bacteria and/or algae in the solution. Examples of suitable humectants
are, propan-1,2-diol, butan-1,2-diol, butan-2,3-diol and butan-1,3-diol,
urea, caprolactam and polyethylene glycols.
When the medium comprises water and one or more water-soluble organic
solvent(s) it preferably contains a dispersing agent and a defoamer.
Suitable dispersing agents include for example, lignosulphonates, a
naphthalene, sulphonic acid/formaldehyde condensate and a
phenol/cresol/sulphanilic acid/formaldehyde condensate. The dispersing
agent is preferably present at from 0.05 to 20%, based upon the total
weight of the ink composition.
Suitable defoamers include, for example, nonanol and silicon based mineral
oils. The defoamer is preferably present at from 0.05 to 20% based upon
the total weight of the ink composition.
In view of the foregoing preferences a preferred ink composition comprises
(a) 0.5 to 20 parts of the dye or the mixture of dyes;
(b) 2 to 60 parts of water-soluble organic solvent(s);
(c) 1 to 95 parts water;
(d) 0.5 to 20 parts dispersing agent; and
(e) 0.05 to 2 parts defoamer;
wherein the parts (a)+(b)+(c)+(d)+(e)=100.
In addition to the parts (a) to (e) the ink may contain other components
conventionally use ink jet ink formulations such as a biocide,
surfactants, viscosity modifiers, corrosions inhibitors and kogation
reducing additives.
Examples of further suitable ink media are given in U.S. Pat. No.
4,963,189, U.S. Pat. No. 4,703,113, U.S. Pat. No. 4,626,284 and EP
4,251,50A which are incorporated herein by reference thereto.
When the liquid medium comprises an organic solvent, the solvent is
preferably selected from ketones, alkanols, aliphatic hydrocarbons,
esters, ethers, amides or mixtures thereof. Where an aliphatic hydrocarbon
is used as the solvent a polar solvent such as an alcohol, ester, ether or
amide is preferably added. Preferred solvents include ketones, especially
methyl ethyl ketone and alkanols especially ethanol and n-propanol.
When the liquid medium is an organic solvent it is preferred that the dye
has a solubility of around 10% or more to allow the preparation of
concentrates which may be used to prepare more dilute inks and to minimise
the chance of precipitation of dye if evaporation of the liquid medium
occurs during use of the ink.
Solvent based ink compositions are used where fast drying times are
required and particularly when printing onto hydrophobic substrates such
as plastics, metal or glass.
When the medium for the ink composition comprises a low melting point solid
the melting point of the solid is preferably in the range from 60.degree.
C. to 125.degree. C. Suitable low melting point solids include long chain
fatty acids and alcohols, preferably those with C.sub.18-24 chains, or
sulphonamides. The dye of Formula (1) or mixtures of dyes of Formulae (1)
and (4) or mixture of dyes of Formulae (1) and (5) may be dissolved in the
low melting point solid or may be finely dispersed in it.
It is preferred that the medium is a liquid medium, more preferably a
mixture of water and one or more water-soluble organic solvent(s).
It is preferred that the pH of the ink composition is less than 7, more
preferably in the range from 2 to 6.5 and especially from 4 to 6.
According to a fourth aspect of the present invention there is provided a
process for printing a substrate with an ink composition using an ink jet
printer, characterised in that the ink composition is as hereinbefore
defined for the first, second or third aspects of the present invention.
A suitable process for the application of an ink composition as
hereinbefore described comprises forming the ink into small droplets by
ejection from a reservoir through a small orifice so that the droplets of
ink are directed at a substrate. This process is commonly referred to as
ink jet printing, and preferred ink jet printing processes for the present
inks are piezoelectric ink jet printing and thermal ink jet printing. In
thermal ink jet printing, programmed pulses of heat are applied to the ink
in the reservoir by means of a resistor adjacent to the orifice, during
relative movement between the substrate and the reservoir.
The substrate used in the ink jet printing process is preferably paper, a
plastic, a textile material, metal or glass and is more preferably paper,
plastic or a textile material.
Preferred textile materials are natural, semi-synthetic or synthetic
material. Examples of natural textile materials include wool, silk, hair
and cellulosic materials, particularly cotton, jute, hemp, flax and linen.
Examples of synthetic and semi-synthetic materials include polyamides,
polyesters, polyacrylonitriles and polyurethanes.
Preferred papers are plain and treated papers which may have an acid,
alkaline or neutral character.
Especially preferred substrates include overhead projector slides, plain
and treated papers and synthetic or semi-synthetic textile materials, for
example a polyester.
The preferred ink compositions used in the process is as hereinbefore
described.
According to a fifth aspect of the present invention there is provided a
paper, an overhead projector slide or a textile material printed with an
ink composition according to the first, second or third aspects of the
present invention or by means of the process according to the fourth
aspect of the present invention.
According to a sixth aspect of the present invention there is provided a
process for the coloration of a textile material with any of the ink
compositions according to the first, second or third aspects of the
present invention which comprises the steps:
i) applying the ink composition to the textile material by ink jet
printing; and
ii) heating the textile material at a temperature from 50.degree. C. to
250.degree. C. to fix the dye on the material.
The process for coloration of a textile material by ink jet printing
preferably comprises a pre-treatment of the textile material with an
aqueous pretreatment composition comprising a water-soluble acid and a
thickening agent followed by removing water from the pre-treated textile
material to give a dry pre-treated textile material which is subjected to
ink jet printing in step i) above.
The pre-treatment composition preferably comprises a solution of the acid
in water containing the thickening agent.
The acid is present in the pretreatment composition to provide a pH of less
than 7, preferably a pH in the range of 2 to 6, on the surface of the
fabric. The acidic medium on the surface of the fabric ensures that the
dye chromophore is not decomposed during the dyeing process, as can be the
case if the pH exceeds 7. It is preferred that the acid is a non volatile
acid, more preferably a non volatile organic acid, for example, citric
acid or tartaric acid. The acid is present in the pre-treatment
composition at a concentration sufficient to give a pH in the range of 2
to 6. When the acid is citric or tartaric acid it is convenient to use a
concentration of from 1% to 5% based upon the total weight of the
pre-treament composition.
The thickening agent may be any thickening agent suitable for use in the
preparation of print pastes for the conventional printing of cellulose
reactive dyes. Suitable thickening agents include alginates, especially
sodium alginate, xantham gums, monogalactam thickeners, polysaccharides
and cellulosic thickeners. The amount of the thickening agent can vary
within wide limits depending on the relationship between concentration and
viscosity. However, sufficient agent is preferred to give a viscosity from
10 to 1000 mPa.s, preferably from 10 to 100 mpa.s, (measured on a
Brookfield RVF Viscometer). For an alginate thickener this range can be
provided by using from 10% to 20% by weight based on the total weight of
the pretreatment composition.
The remainder of the pretreatment composition is preferably water, but
other ingredients may be added to aid fixation of the dye to the textile
material or to enhance the clarity of print by inhibiting the diffusion
(migration) of dye from coloured areas to non-coloured areas before
fixation.
Examples of fixation enhancing agents are cationic polymers, such as a 50%
aqueous solution of a dicyanamide/phenol formaldehyde/ammonium chloride
condensate e.g. MATEXIL.TM. FC-PN (available from ICI), which have a
strong affinity for the textile material and the dye.
Examples of anti-migration agents are low molecular weight acrylic resins,
e.g. polyacrylates, such as poly(acrylic acid) and poly(vinyl acrylate).
In the pre-treatment stage of the present process the pre-treatment
composition is preferably evenly applied to the textile material. Where a
deeply penetrated print or a deep shade is required the pre-treatment
composition is preferably applied by a padding or similar process so that
it is evenly distributed throughout the material. However, where only a
superficial print is required the pretreatment composition can be applied
to the surface of the textile material by a printing procedure, such as
screen or roller printing, ink jet printing or bar application.
In the pre-treatment stage of the present process, water may be removed
from the pre-treated textile material by any suitable drying procedure
such as by exposure to hot air or direct heating, e.g. by infra-red
radiation, or micro-wave radiation, preferably so that the temperature of
the material does not exceed 100.degree. C.
The application of the ink composition to the textile material, stage (i)
of the present process, may be effected by any ink jet printing technique,
whether drop on demand (DOD) or continuous flow. Where the ink jet
printing technique involves the charging and electrically-controlled
deflection of drops the composition preferably also contains a conducting
material such as an ionised salt to enhance and stabilise the charge
applied to the drops. Suitable salts for this purpose are alkali metal
salts of mineral acids.
After application of the ink composition, it is generally desirable to
remove water from the printed textile material at relatively low
temperatures (<100.degree. C.) prior to the heat applied to fix the dye on
the textile material as this has been found to minimise the diffusion of
the dye from printed to non-printed regions. As with the pretreated
textile material removal of water is preferably by heat, such as by
exposure to hot air or to infra-red or micro-wave radiation.
In stage (ii) of the present process, the printed textile material is
submitted to a short heat treatment, preferably after removal of water by
low-temperature drying, at a temperature from 100.degree. C. to
200.degree. C. by exposure to dry or steam heat for a period of up to 20
minutes in order to fix the dye on the textile material. If a steam (wet)
heat treatment is used, the printed material is preferably maintained at
100.degree.-105.degree. C. for from 5 to 15 minutes whereas if a dry heat
treatment is employed the printed material is preferably maintained at
140.degree.-160.degree. C. for from 2 to 8 minutes.
After allowing the textile material to cool, unfixed dye and other
ingredients of the pretreatment and dye compositions may be removed from
the textile material by a washing sequence, involving a series of hot and
cold washes in water and aqueous detergent solutions before the textile
material is dried.
Preferred textile materials for use in the process according to the sixth
aspect of the present invention are as hereinbefore defined for the fourth
aspect of the present invention.
According to a seventh aspect of the present invention there is provided a
textile material, especially a synthetic or semisynthetic textile
material, coloured an by means of the process according to the sixth
aspect of the present invention.
According to an eighth aspect of the present invention there is provided a
toner resin composition comprising a toner resin and a dye, characterised
in that the dye is of Formula (1), a mixture of dyes of Formulae (1) and
(4) or a mixture of dyes of Formulae (1) and (5).
The toner resin is preferably a thermoplastic resin for example, a styrene
or substituted styrene polymer or copolymer, for example, a polystyrene or
styrene-butadiene copolymer, especially a styrene-acrylic copolymer, for
example, a styrene-butyl methacrylate copolymer. Other suitable toner
resins include polyesters, polyvinylacetate, polyalkenes,
polyvinylchloride, polyurethanes, polyamides, silicones, epoxyresins and
phenolic resins. Examples of toner resins are given in Electrophotography
by R. M. Scharfert (Focal Press), U.S. Pat. No. 5,143,809, UK 2090008,
U.S. Pat. No. 4,206,064 and U.S. Pat. No. 4,407,928 which are incorporated
herein by reference thereto.
The toner resin composition preferably contains from 0.1% to 20% of the dye
of Formula (1), a mixture of dyes of Formulae (1) and (4) or mixture of
dyes of Formulae (1) and (5), more preferably from 3% to 10% based on the
total weight of the toner resin composition.
The toner resin composition may be prepared by any method known to the art
which typically involves mixing the toner resin with an optional charge
control agent (CCA) and the dye of Formula (1) a mixtures of dyes of
Formulae (1) and (4) or a mixture of dyes of Formulae (1) and (5), by
kneading in a ball mill above the melting point of the resin.
Generally, this involves mixing the molten toner resin composition for
several hours at temperatures from 120.degree. to 200.degree. C., in order
to uniformly distribute the optional CCA and dye throughout the toner
resin. The toner resin is then cooled, crushed and micronised until the
mean diameter of the particles is preferably below 20 .mu.m and, for high
resolution electro-reprography, more preferably from 1 to 10 .mu.m. The
powdered toner resin composition so obtained may be used directly or may
be diluted with an inert solid diluent such as fine silica by mixing for
example in a suitable blending machine.
It is preferred that when a CCA is present in the toner, it is present at
from 0.1 to 5% based upon the total weight of the toner.
The CCA may be any known positive or negative charge control agent.
Examples of negative charge control agents include metal complexes of azo
dyes, preferably 2:1 complexes with chromium (III), cobalt (III) and iron
(III). Preferred azo dyes are 1-phenylazo-2-naphthol dyes. Examples of
positive CCA's include nigrosine dyes, phenazines, triphenylmethane dyes,
2:1 chromium complexes of an aromatic orthohydroxy carboxylic acid such as
BONTRON.TM. E81 and BONTRON.TM. E82 (commercially available from Orient
Chemical Industries) and alkyl pyridinium halides such as cetyl pyridinium
chloride. It is preferred that the CCA used in the toner is colourless or
substantially colourless such that the colour of the toner is not markedly
effected by the presence of the CCA.
Further suitable examples of CCA's are described in WO 94/23344 which is
incorporated herein by reference thereto.
The invention is further illustrated by the following Examples in which all
parts and percentages are by weight unless otherwise stated.
EXAMPLE 1
Preparation of:
##STR7##
Sodium nitrite (3.22 g) was added to concentrated sulphuric acid (20
cm.sup.3) and the mixture heated to 70.degree. C. and then cooled to
5.degree. C. Further concentrated sulphuric acid (15 cm.sup.3) was added
followed by (25 cm.sup.3) of a 86:14 mixture of acetic acid and propionic
acid. 2-Amino-3-acetyl-5-nitrothiophene (8.5 g) was then added slowly
below 0.degree. C. and the mixture stirred at -2.degree. C. to 0.degree.
C. for 2 hours and then 0.degree. C. to 2.degree. C. for 3 hours when
diazotisation was complete. The solution was then added to a mixture of
3-N,N-diethylaminoacetanilide (10.3 g), methanol (75 cm.sup.3), crushed
ice (180 g) and sulphamic acid (1.0 g). The temperature was maintained at
0.degree.-5.degree. C. and the pH at 1-2 by the addition of sodium acetate
solution. The mixture was stirred at 0.degree.-5.degree. C. for 2 hours
and then the product was isolated by filtration and washed with water.
Yield after drying 12.9 g.
EXAMPLES 2 to 15
Dyes of the formula:
##STR8##
wherein the substituents A to G are shown in Table 1 may be prepared using
an analogous process to that described in Example 1.
TABLE 1
__________________________________________________________________________
Eg
A B C D E F G
__________________________________________________________________________
2 --NO.sub.2
H --COCH.sub.3
--CH.sub.3
--C.sub.2 H.sub.5
--(CH.sub.2).sub.4 OCOCH.sub.3
H
3 --NO.sub.2
H --COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.5
--(CH.sub.2).sub.4 OCOCH.sub.3
H
4 --NO.sub.2
H --COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.5
--C.sub.2 H.sub.4 OH
H
5 --NO.sub.2
H --COC.sub.2 H.sub.5
--NHCOCH.sub.3
--C.sub.2 H.sub.4 OH
--C.sub.2 H.sub.4 OH
H
6 --NO.sub.2
H --COC.sub.2 H.sub.4 OH
--NHCOC.sub.2 H.sub.5
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
H
7 --NO.sub.2
H --COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.4 OCH.sub.3
--C.sub.2 H.sub.5
H
8 --NO.sub.2
H --COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.4 OCOCH.sub.3
--C.sub.2 H.sub.4 OCOCH.sub.3
H
9 --NO.sub.2
H --COCH.sub.3
--CH.sub.3
--C.sub.2 H.sub.5
--(CH.sub.2).sub.4 OCOCH.sub.3
--CH.sub.3
10
--NO.sub.2
H --NO.sub.2
--NHCOCH.sub.3
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
H
11
--NO.sub.2
H --COCH.sub.3
--CH.sub.3
--C.sub.2 H.sub.5
--(CH.sub.2).sub.2 OCOCH.sub.3
H
12
--NO.sub.2
H --COCH.sub.3
--OCH.sub.3
--C.sub.2 H.sub.4 OH
--C.sub.2 H.sub.4 OH
--OCH.sub.3
13
H --CN
--COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
H
14
--NO.sub.2
H --COCH.sub.3
--NHCOCH.sub.3
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
--CH.sub.3
15
--NO.sub.2
H --NO.sub.2
H --C.sub.2 H.sub.4 OCOCH.sub.3
--C.sub.2 H.sub.4 OCOCH.sub.3
H
__________________________________________________________________________
EXAMPLES 16 to 21
Dyes of Formula (5) with the substituents R.sup.9 to R.sup.15 shown in
Table 2 may be prepared by diazotising the aniline of formula:
##STR9##
and coupling the diazo salt with the compound of the formula:
##STR10##
TABLE 2
__________________________________________________________________________
Eg
R.sup.9
R.sup.10 R.sup.11
R.sup.12
R.sup.13
R.sup.14
R.sup.15
__________________________________________________________________________
16
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
--NO.sub.2
--NO.sub.2
--CN
--CH.sub.3
H
17
--C.sub.2 H.sub.5
--(CH.sub.2).sub.4 OCOCH.sub.3
--Br
--CN
--Cl
--CH.sub.3
--CH.sub.3
18
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
--CN
--CN
--NO.sub.2
H --OCH.sub.3
19
--C.sub.2 H.sub.4 OH
--C.sub.2 H.sub.5
--H --NO.sub.2
--CN
--OCH.sub.3
--OCH.sub.3
20
--C.sub.2 H.sub.4 OH
--C.sub.2 H.sub.4 OH
--CN
--NO.sub.2
--CN
--CH.sub.3
H
21
--C.sub.2 H.sub.5
--C.sub.2 H.sub.5
--CN
--NO.sub.2
--Br
--NHCOCH.sub.3
H
__________________________________________________________________________
EXAMPLE 22
The following ink compositions containing the dyes and mixtures thereof,
described in the previous examples may be prepared according to the
formulations shown in Table 3 wherein the figures denote parts by weight
based upon the total weight of the ink composition.
In Table 3 Formulations A and B refer to the following ink media wherein
the parts are by weight based upon the total weight of the ink
composition.
______________________________________
Formulation A
Glycerol 10.0 parts;
2-pyrrolidone 5.0 parts;
Nonanol (defoaming agent)
0.5 parts;
Lignosulphonate (dispersing agent)
5.0 parts; and
Proxel .TM. GXL (a biocide available from
0.1 parts
Zeneca Limited)
Formulation B
Ethylene glycol 10.0 parts;
N-methylpyrrolidone 5.0 parts
Sodium Dispersol (a dispersing agent available from
5.0 parts;
Zeneca Limited)
Proxel .TM. GXL (a biocide available from
0.1 parts; and
Zeneca Limited)
Nonanol 0.5 parts
______________________________________
Each ink composition shown in Table 3 has 100 parts, the balance being
water (i.e. 100--dye parts--formulation parts).
The ink compositions shown in Table 3 may be applied to a substrate such as
paper using an ink jet printer.
TABLE 3
______________________________________
Dye(s) from
No. Parts of
Example(s)
Dye(s) Formulation
Balance of water (parts)
______________________________________
1 5 A 74.4
1 10 A 69.4
1 2 B 77.4
1 5 B 74.4
1 8 B 71.4
1 (50%)
5 A 74.4
16 (50%)
1 (50%)
6 A 73.4
20 (40%)
1 (65%)
3 B 76.4
21 (35%)
2 (50%)
2.5 A 76.9
1 (50%)
1 (55%)
8.9 B 70.5
3 (45%)
1 (70%)
10.0 A 69.4
6 (30%)
1 (80%)
1.5 A 77.9
4 (20%)
1 (90%)
3.6 B 75.8
10 (10%)
1 (77%)
7.0 A 72.4
14 (23%)
______________________________________
When a mixture of dyes is used in the ink formulation, the weight ratio of
the dyes in the mixture is shown in brackets in Table 3 in the column
marked "Dye(s) from Example(s) of Table 3". Thus the mixture 1 (50%), 16
(50%) refers to a 50:50 mixture of the dye from Example 1 and the dye from
Example 16.
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